New Paper:Labile Cu(I)-Catalyst/Spectator Cu(II)-Species in Copper-Catalyzed C-C Coupling Reaction: Operando IR, In situ XANES/EXAFS Evidence and Kinetic Investigations

New Paper:Labile Cu(I)-Catalyst/Spectator Cu(II)-Species in Copper-Catalyzed C-C Coupling Reaction: Operando IR, In situ XANES/EXAFS Evidence and Kinetic Investigations

Chuan He,a Guanghui Zhang,a,b Jie Ke,a Heng Zhang,a Jeffrey T. Miller,b Arthur J. Kropf,b and Aiwen Lei*,a,b

aCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, P. R. China;

bChemical Science and Engineering Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL 60439, USA.

J. Am. Chem. Soc.2013, ASAP

DOI: 10.1021/ja310111p

http://pubs.acs.org/doi/abs/10.1021/ja310111p

ABSTRACT: Insights toward the Cu-catalyzed C-C coupling reaction were investigated through operando IR and in situ XANES/EXAFS. It was found that the Cu(I)-complex formed from the reaction of CuI with β-diketone nucleophile was liable under the cross-coupling conditions, which is usually considered as active catalytic species. This labile Cu(I)-complex could rapidly disproportionate to the spectator Cu(II) and Cu(0) species under the reaction conditions, which was an off-cycle process. In this copper-catalyzed C-C coupling reaction, β-diketone might act both as the substrate and the ligand.